WO1985001155A1

WO1985001155A1 - Iodine cell

Info

Publication number: WO1985001155A1
Application number: PCT/JP1984/000416
Authority: WO
Inventors: Sadao Kobayashi; Hiroshi Sukawa; Sadaaki Yamamoto
Original assignee: Mitsui Toatsu Chemicals, Inc.
Priority date: 1983-08-30
Filing date: 1984-08-30
Publication date: 1985-03-14
Also published as: EP0161318A4; EP0161318B1; US4656105A; EP0161318A1

Abstract

An iodine cell which has a depolarizing mix for cell positive electrode obtained in such a manner that a composite formed by setting iodine by means of a polymer having an ability to form a complex adduct in cooperation with iodine is allowed to dipersedly contain a carbonaceous material, such as carbon black or graphite. The iodine cell preferably employs a cation exchanger film as a separator. The iodine cell features high output, low internal resistance, high charging/discharging life (a high number of cycles), and long life and advantageously permits charging even in a state wherein almost all the iodine has been desorbed from the positive electrode. It is possible to use the iodine cell for a primary battery, more preferably a secondary battery.

Description

Specification

Iodine battery

〔Technical field〕

The present invention relates to an iodine battery in which iodine is immobilized with a polymer and used as a positive electrode active material.

[Background art]

Iodine is a substance that is easy to form as an anion] and is one of suitable ones as a positive electrode active material. This iodine is known to form a charge-transfer complex with various organic substances. The charge-transfer isomers of iodine are iodine (acceptor) and various electron-donating organic compounds (one component of organic donors). 9 J, electron-donating compounds are heterocyclic compounds such as phenothiazine and carpazol; . Ren, Multi ¾ aromatic compounds such as peri Ren;? And Helsingborg - 2 - Binirupiri Uz down, volume triethylene, volume Li acetylene, 7j Li Ha ⁰ Rafeniren, 7j Li Choi two Ren, Li arsenide. Rolls, polyethers, polyanilines, polyamides, polybinore alcohols, polyethylene, and borifs. Mouth-organic polymers such as bilen and polystyrene are known.

Some batteries using these iodine charge-moving complexes (hereinafter referred to as iodine complexes or simply complex adducts) as a main component of a positive electrode mixture are also known. Further, the present inventors have found that organic polymers such as urea-formaldehyde resin, polyurethane, polyacrylonitrile, polyacrylamide, polymethacrylamide, polyether, and melamine bitumen are also used as organic donor components. Found to be effective.

However, a battery using such an iodine complex as a positive electrode active material has a low output, and as iodine is lost as the battery is discharged, the electrical conductivity sharply decreases, and the resistance of the positive electrode mixture increases remarkably. The problem was that the resistance increased significantly.

In addition, when the positive electrode mixture obtained from the iodine complex is used in a secondary battery, most of the iodine is released from the positive electrode mixture due to discharge, so that the positive electrode mixture is usually completely isolated. A secondary battery that cannot be recharged has a decisive disadvantage. This is boriamid, boriacrilonitril.

2 - the original ® © boron complex of Bollywood Ma one is an absolute緣体such as bi Ruhi ⁰ Li Mi Uz down was inevitable to occur a problem when there was甩I.

Furthermore, such batteries have the disadvantage that the battery life is short.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a preferred embodiment of the battery of the present invention.

In the figure, 10 is a positive electrode, 20 is a negative electrode, 30 is an electrolyte, and 40 is a cell. Leh data, 5 0 and 5 0 'support 6 0 c ⁰ Kkin, 7 0 denotes, respectively Re their leads. -

(Disclosure of the Invention)

According to the present invention, a complex adduct of iodine and a polymer capable of forming a complex adduct with iodine and / or iodine is dispersed in the polymer. The present invention provides a battery in which the squeezed composition is used as a main component of a positive electrode mixture, wherein the positive electrode mixture contains carbons in a dispersed state.

In the present invention, the polymers capable of forming a complex adduct with iodine include polyacrylamide, polymethacrylamide, urea-formaldehyde tree, polyvinyl alcohol, poly (vinyl acetate), nalon-6, and nairon. -6.6, Nylon-12, Nylon-6.9, Nylon-6.10, etc. Aliphatic boramides, wholly aromatic boramides, such as Kevlar (Dupont's product trademark), Boljylene, Poly Propylene, polystyrene, polyethane, melamine resin, polyether, polyacrylonitrile, pallets resin, polymethyl methacrylate, borotetramethylene ether, polyvinyl acetate. Mouth Li Dong, Boli-4-Bürch. Rein, Bol-2-Bilhi. Resin, poly-N-bulcarpazole and the like are mentioned as preferable ones, but the above-mentioned known polymers can of course be used.

These may be used as a blend of two or more kinds, or a copolymer thereof may be used. '

In the battery of the present invention, as described above, carbon is dispersedly contained in a positive electrode mixture composed of a polymer and iodine capable of forming a complex adduct with iodine. The method is, for example, as follows.

First, carbon is added to a predetermined amount of a polymer capable of forming an adduct of a complex with iodine to contain the same in a dispersed state. As a method for adding the carbons, it is preferable to prepare a polymer-carbon composite in advance. This includes Bolima I

OMPI

d WIPO Is dissolved in a solvent, carbons are added to the mixture, and then mixed, and then the solvent is removed. Alternatively, carbons are directly kneaded and dispersed in a polymer. Iodine is added to the thus obtained Bolimar carbon complex. As the iodine, ordinary solid or flake-like iodine is used as it is or is refined as necessary. As a method of adding iodine,

(i) A method of adding and adsorbing iodine vapor to the polymer-carbon composite as described above by contacting with iodine vapor; (ii) adding the polymer-carbon composite to a solution of iodine-containing benzene, acetate, etc. Addition of iodine by immersion * Adsorption method, Gii) or method of kneading iodine into the volima-carbon complex. Instead of preparing a carbon composite in advance, a method is also used in which carbon and iodine are simultaneously added to a predetermined amount of polymer and melted and kneaded in a dispersed manner to produce a positive electrode mixture in one step. Is done. In this case, there is no particular restriction on the order of addition or mixing of the materials added for kneading.

In other words, in short, a complex adduct of a polymer and iodine and a composition in which carbons are dispersed in a dispersion composition of phosphorus or iodine, that is, a composite (positive electrode mixture) are substantially used. It only needs to be able to be made, and the method of making it is not particularly limited. Of course, this manufacturing method also includes a method in which a current collector is incorporated into the positive electrode mixture in order to quickly extract electricity from the positive electrode mixture. .

As the current collector, J9 is also a precious metal other than the metal used for the negative electrode, such as platinum or stainless steel net, carbon mat, cloth, and porous metal.

OMPI

. WIPO-I, J A shape such as a rack is used.

Examples of carbons added to the positive electrode mixture in the battery of the present invention include carbon black, acetylene black, graphit, and ketjen plaque (trademark of Zuri Co., Ltd.). A fiber-like shape that is easily dispersed is preferably used. The amount of carbon used depends, of course, on the type of carbon, but it is usually 0.5 to 60% (weight, below) for the polymer to be added. 5% to 5%], and it is 0.5 to 40% for pulverized Dalafite. At this value, the effect of addition is small, and the conductivity decreases sharply at low iodine contents. Further, even if it is used beyond the above value, the effect is not further improved and the formability is deteriorated. For Ketjen Black, for example, 5 to 40% is more preferable, and 10 to 30% is particularly preferable.

In order to form the battery of the present invention, iodine prepared as described above, a complex adduct of iodine with a polymer capable of forming an adduct with iodine, and Z or iodine is added to the polymer. What is necessary is just to make the positive electrode a mixture containing the dispersed composition as a positive electrode mixture, and make the negative electrode a metal such as lithium, zinc, cadmium, magnesium, aluminum or the like, and bring them into contact with each other.

In the battery of the present invention, iodine is assumed to be mostly in the form of a complex adduct in the polymer, and it is, of course, necessary that all of the iodine be present as a complex activator. Some or all of them may simply be dispersed in free form in the polymer. In short, iodine All that is required is that it be substantially incorporated into Lima. In the case of a normal battery, the positive electrode and the negative electrode are usually brought into contact via an electrolyte, but the battery of the present invention is not necessarily required to have such an electrolyte. It is presumed that this is because the metal iodide generated on the side of the interface where both electrodes come into contact with each other; constitutes the electrolyte. Thus, it can be fully used for applications that require such a large output, such as cardiac pacemakers. Further, it is also possible to supply a solid electrolyte such as lithium iodide and iodine from the beginning.

Further, in the case of a wet type secondary battery (storage battery) having an electrolyte solution, an electrolyte solution of metal iodide (for example, subweight iodide if the anode metal is sub-promotion) is used as a discharge product corresponding to the metal of the anode. The positive electrode and the negative electrode may be brought into contact through the intermediary.

Of course, in addition to the metal iodide electrolytes generated by the discharges described above, ammonium chloride, sodium iodide, sodium chloride, sodium halide, sodium halide, potassium halide, lithium iodide, etc. An electrolyte solution such as iodide may be used as the auxiliary electrolyte. In addition, to prevent self-discharge, porous seha. It is also preferable to volatilize between both active materials in the refining solution.

The method for forming the storage battery of the present invention will be described in more detail. The electrode formed by integrating the current collector with the composition (composite) of the polymer, carbon and iodine obtained as described above. The positive electrode is made of a metal as described in the section of the formation of the battery, and the metal corresponding to each metal of the negative electrode is used as the negative electrode. It is only necessary to assemble the oxidized image (for example, zinc iodide when the negative electrode metal is 15) as the electrolyte. Of course, the auxiliary electrolyte may be used as a substitute for the metal iodide, if necessary, or the auxiliary electrolyte may be added to the metal iodide. Such an electrolyte is usually used by dissolving it in water. In some cases, for example, when the negative electrode is a metal that reacts violently with water, such as lithium sodium, the propylene power is used. It is desirable to use a solvent with low reactivity such as one-port r-butyl lactone. In addition, metal iodide dissolved in these solvents is used by impregnating it with a porous material such as glass short olives (which may be paper) that has a large liquid holding capacity. It is preferred that Such a porous material impregnated with an electrolyte has an advantage that a storage battery can be assembled as it is between the positive electrode and the negative electrode.

By discharging the storage battery formed as described above, iodine ions are generated at the negative electrode when the metal ion force is positive, and these combine to form a metal iodide that is an electrolytic poor (discharge product). . At the time of charging, the metal iodide is decomposed into metal and iodine, and the metal is deposited on the negative electrode. On the other hand, iodine is trapped in the positive electrode mainly composed of boron and lithium. It becomes.

That is, in the storage battery of the present invention, when a DC voltage is applied during charging, iodine is deposited on the positive electrode side, and metal is deposited on the negative electrode side, the iodine deposited on the positive electrode side is volatilized mainly by the positive electrode. And complex adducts easily Formed and included in the polymer. Then, after the charging is completed, by discharging the DC voltage and connecting the bipolar terminals via the load, the discharge occurs, and power is obtained in the load.

The battery of the present invention is characterized in that carbon is dispersed in a positive electrode mixture containing iodine and a specific polymer complex adduct and a composition in which iodine is dispersed in Z or the polymer as a main component. It is characterized by being contained. The technical intention of dispersing this carbon is as follows. As described above, it has been known that complex adducts of iodine and certain bolimers have poorer electrical conductivity than each single substance. -2-The iodine complex of vinyl viridine is used as a positive electrode mixture for primary batteries for heart manufacturers. However, these complex adducts have the drawback that, as they discharge, the iodine is lost and the electrical conductivity is sharply reduced, and the internal resistance of a battery using this is significantly increased. In particular, when this rat body adduct is used in the positive electrode mixture of a secondary battery, the amount of iodine in the positive electrode mixture is extremely small due to discharge. As described above, it was impossible to fulfill the charge because it was completely lost. That is, such a complex adduct could not be used at all as a secondary battery.

However, in the battery of the present invention, by dispersing carbons from the polymer adduct into the main positive electrode mixture, it is possible to form a highly conductive positive electrode mixture, and the discharge proceeds. Even inside the positive electrode side A remarkable effect that a large current can be obtained with little increase in resistance can be obtained.

Surprisingly, by adding carbons to the complex adduct, the electrical conductivity of the positive electrode mixture may even increase due to discharge.

As described above, the addition of carbons to the positive electrode mixture according to the present invention is necessary for the complex battery of the present invention. .

In a preferred embodiment of the present invention, a conventional porous seha. A cation exchange membrane is introduced into the electrolyte solution instead of the rotor. In this way, the traditional Serra. When using a writer: In comparison, the battery life can be greatly extended. It seha yang ion exchange membrane. The iodine (/ ₂ ), which is the positive electrode active material immobilized as a complex, reacts with the metal iodide () in the electrolytic solution to form a negative electrode. It is presumed that self-discharge, which may occur in contact with metal, can be prevented very effectively.

In the battery of the present invention, the cell. The cation-exchange membrane used as a collector may be either an inorganic poor type membrane or an organic type membrane. In particular, among the inspected types, a hydrocarbon-ion type ion exchange membrane and a fluorocarbon type membrane can be used. Zion exchange membranes are preferred. -Naturally, the cation exchange membrane selectively permeates only cations, but the cation exchange groups used in the battery of the present invention include sulfonic acid groups, Either sulfonic acid group or phosphoric acid group It may be an exchange group.

Usually, a surface treatment is appropriately performed to reduce the electric resistance of the film, and a cloth or a rope is used to enhance the mechanical strength.

As the cation exchange membrane provided for the * pond of the present invention, a commercially available one can be used as it is, provided that the above conditions are satisfied. For example, if it is a hydrocarbon type, if it is a selemion cation exchange membrane C f (made by Asahi: ^ 子), a cation exchange membrane d (made by Kuriyo Kagaku Sho 棻), or if it is a fluorocarbon type Nafion 3 2 4 cation exchange membrane (made by Dubon Co., Ltd.) is a cation that selectively permeates cations and selectively blocks anion transmission. Anything is acceptable, especially if not limited to these. Thus, as a preferable cation exchange membrane, a membrane having low air resistance, high mechanical strength, and strong corrosion resistance in a redox atmosphere is of course preferable.

[Best mode for carrying out the invention]

Example 1

A battery having the configuration shown in FIG. 1 was assembled as follows.

Ketjen 'Black KB-EC (trademark of STZO) of DMF 6 Qιφ containing polyacrylonitrile (average molecular weight: 150,000) 300 was added and dispersed well. The thing in diameter ⁴ 5 cm of the disk-shaped carbon fiber (Kureha Chemical Co., Ltd. - T 1 5). To the coating, removing ¾ natural evaporation Nyo. Furthermore, by immersing in iodine acetone solution] Used as positive electrode lo. As the negative electrode 20, an α 3 plate (Mitsui Kinzoku Co., Ltd.) was used. The electrolytic solution was a 1 mol / ^ aqueous solution of N, which was impregnated with ² glass fibers ^ paper ³⁰ ^ ² , during which time the cell was washed. Tucked the Seremi on腠manufactured by Asahi Glass child (Ltd.) as Lake ⁴ 0. This was placed in the two poles, “No. 1” and the battery was used. In FIG. 1, 50 and 5 are a support, 60 is a hook, and 7 ′ 0 is a lead wire.

The experiment was performed under a nitrogen stream at 25 and the initial short-circuit current (/ S c) at the time of discharge was measured and found to be 80 τηΑ / cm ² . The open-circuit voltage at this time: 1. was ³ 6. The battery was discharged to a cut-off voltage of 0.9 under the condition of 2U ¾ current, and then charged and discharged to a cut-off voltage of 1.5.

Even after 600 cycles, the energy efficiency and current efficiency remained almost unchanged. The electric capacity after 600 cycles with respect to the initial capacity was 87. This indicates that this battery is practically at the same level as a dual battery.

For comparison, a battery was prepared in exactly the same procedure as above except that a positive electrode mixture containing Ketjen's plaque B-^ (was used.] 7, and the battery was evaluated under the same conditions. When the initial short-circuit current (/ sc) at time 測定 was measured, it was S mA / cm ^z , and the open-circuit voltage at this time was 1.34. After discharge, charging was attempted, but the voltage rose sharply and the battery could not be charged. A mixture of 2,4-trilendiene sociate and 2,6-trilendiene sociate (Mitsui Nisso Urethane (侏) ΓZ) / -80Z20) The propylene glycol 0.9- ^ containing Ketjen Black KB-was well mixed to synthesize a polyurethane resin composition. The polyurethane resin composition ³⁰ was dissolved in phenol to obtain a mixture. This in diameter ⁴ ⁵ cm of the disk-shaped carbon fiber (Kureha) made -. 7

15) Apply to, and remove phenol by evaporation method. This was immersed in an iodine acetate solution to add iodine 120 and used as a positive electrode. As the negative electrode, a 0-3 thick zinc plate (made by Mitsui Kinzoku) was used. Electrolyte in 1 mode ^ / Les / I aqueous solution of N _4, which was 2 S-containing two glass fiber ^ paper, Serra therebetween. Serumion 製 made by Asahiko (pearl) was inserted as a recorder. The battery was inserted between the two. The structure of the battery is the same as that of the first embodiment, as shown in FIG. The experiment was performed at 25 ° C. under a nitrogen stream, and the initial short-circuit current (/ sc) at the time of discharge was measured, and it was 42 / cm ² . The open-circuit voltage at this time was 1.36. The battery was discharged to a final voltage of 0.9 under the conditions of Z constant flow, and then charged and discharged to a final voltage of 1.5.

Even after 600 cycles, the energy efficiency and the current efficiency were almost unchanged. The electric capacity after 600 cycles with respect to the initial capacity was 87 '. This indicates that this battery is actually at a practical level as a secondary battery. For comparison, Ketjen Black KB-(A battery was prepared in exactly the same procedure as above except that a positive electrode mixture without the addition of 7 was used, and evaluated under the same conditions. Initial short circuit during discharge of this battery the measured current (sc), was 6 m Α / αη ^ζ. the open circuit voltage at this time was 1.3 4. where a single further Gyoru charge and discharge test, after the discharge has been attempted to charge The voltage rises so steeply that it cannot be charged.

Example 3

To a formic acid solution containing Nylon- ⁶ (manufactured by Toray Industries, Inc.) 300), 60 ^ ketchene * black KB-EC (trade name of ZO Corporation) was added and well dispersed. This is applied to a disk-shaped carbon fiber with a diameter of 4.5 (product of Kureha Chemical Co., Ltd.-715), and formic acid is removed by a natural evaporation method. This was immersed in an iodine-acetone solution], and iodine 360 ^ was added, and used as a positive electrode. A 0.3-inch thick zinc plate (made by Mitsui Kinzoku (Δ)) was used as the negative electrode. The electrolyte is a 1 molar Z aqueous solution of N 4 CZ, which is impregnated with two pieces of glass braided paper, and between which the cell is sewn. A SELIMION CJi film manufactured by Asahi Glass Co., Ltd. was sandwiched between them. This was inserted between both sides to form a battery. The configuration of the battery is the same as that of Example 1 as shown in FIG. The experiment was performed at 25 ^U C under a nitrogen stream, and the initial short-circuit current (/ &) at the time of discharge was measured to be 7 l mAZa ^. The open-circuit voltage at this time: 1. was ³ 6. This battery was charge-discharge 'anonymous test Bokuoku Kaee charged to a final voltage of 1.5 gamma After discharged to a final voltage of ^0.9 under the conditions of 2 constant ¾ stream. 600 Even after the cycle, the energy efficiency and current efficiency remained almost unchanged. The electric capacity after 600 cycles was 85 with respect to the initial capacity. This indicates that this battery is practically at a practical level as a secondary battery.

A battery was prepared in exactly the same procedure as above except that a positive electrode mixture without the addition of Ketjen's plaque-£ C was used for the sake of comparison, and evaluated under the same conditions. When the initial short-circuit W current (/ sc) at the time of discharging of the battery was measured, it was 10 Til A / cm ¹ . The open-circuit voltage at this time was 1.34 mm. Furthermore, when the charge / discharge test was completed, charging was attempted after discharging, but the voltage rose sharply and the charging could not be performed.

Example

Initial reaction of urea resin Euroid # 3 20 (registered mark of Mitsui Kuriatsu Chemical Co., Ltd.), which is a 5 syrup, with iodine 50 and carbon as Ketchen 'Black KB-EC (^ ZO After adding 2Ο and mixing well, 1 drop of 12N hydrochloric acid was added as a hardener and mixed well. The ones, diameter ⁴ ⁵ ^ disk-shaped carbon镞維(Kureha Chemical (su) manufactured - 7 1 5). To the coated fabric was used as a positive electrode is deer. The negative electrode used was 0.3 thigh & plate (manufactured by Mitsui Kinzoku). The electrolyte is an aqueous solution of lithium chloride 20. This is impregnated with 2 pieces of glass fiber ^ paper, and during that time, it is seha. Les tucked the Asahi Glass Co., Ltd. of Selemion film as one data ₀ was the battery put this thing between the two poles. The configuration of the battery is shown in FIG. 1 as in Example 1. It is common.

Experiments conducted under a nitrogen gas stream 2 ⁵ ° C, the discharge time of the initial short-circuit current (/ sc) was measured and found to be 3 5 w ^2. The open-circuit voltage at this time was 1.3 hours. After discharging the battery to a final voltage of 0.9 F under the condition of a constant current of 2 m, a charge / discharge test for charging to a final voltage of 1.5 was repeated. Even after 600 cycles, the energy efficiency and current efficiency were almost unchanged. The electric capacity after 6'00 cycles with respect to the initial capacity was 45. This indicates that this battery is substantially at a practical level as a secondary battery.

For comparison, a battery was prepared in exactly the same procedure as above except that a positive electrode mixture to which Ketjen Black-C was not added was used and evaluated under the same conditions. When the initial short-circuit current (s c) during discharge of this battery was measured,

/ cm ^z . The open-circuit voltage at this time was 1.3. In addition, when a charge / discharge test was performed, charging was attempted after discharging, but the voltage was "intense" and charging failed.

Example 5

Acrylic amide (manufactured by Mitsui Toatsu Chemicals, Inc.) 300 ^ and bismethylene acryloamide 1 are dissolved in sufficiently deoxygenated water, and persulfuric acid monoxide 3 and sodium acid sulfite 1.5 are added thereto. Add 20 in a stream of nitrogen. The mixture was slightly polymerized with C, and Ketjen'Black-C (trademark of AKZ Hisha) was added thereto and kneaded and dispersed. This thing, diameter ^{of 4} ⁵ of the disc IPO,.: Carbon fiber (Kureha Chemical Co., Ltd.-715) was applied and cured to use as a positive electrode. As the negative electrode, 0.3 thick aluminum plate (manufactured by Mitsui Kinzoku Co., Ltd.) was used. The electrolytic solution is an aqueous solution of lithium chloride, which is impregnated with two pieces of glass fiber paper, and then the cell is immersed. As a rake, a Ceremion C i film made by Asahi ^ was inserted. This was placed between the electrodes to make a battery. The configuration of the battery is as shown in FIG. 1 as in Example 1.

Experiments conducted under a nitrogen gas stream 2 5 ° C, the discharge time of the initial short-circuit current (/ sc) was measured, it was 4 6 m A / cm ^z. The open-circuit voltage at this time was 1.3 mm. The battery was discharged under a constant current condition of 2 to a cutoff voltage of 0.9 and then charged and discharged to a cutoff voltage of 1.5. Even after 600 cycles, the energy efficiency and the current efficiency were almost unchanged. The electric capacity after 600 cycles with respect to the initial capacity was 72 ° b. This indicates that this battery is practically at a practical level as a secondary battery.

For comparison, a battery operation was performed in exactly the same procedure as above except that a positive electrode mixture to which Ketjen * Black was added was used, and the battery operation was evaluated under the same conditions. Measurement of the initial short-circuit current during discharge of the ¾ pond (J sc), was 6 m A / cm ^z. The open-circuit voltage at this time was 1.3. In addition, a charge / discharge test was performed. After discharge, the battery tried to be charged, but the voltage rose sharply, and it was difficult to charge.

Example 6 ^ Literamethylene ether (reduced viscosity in 0.1% benzene solution 1.12: Otsu et al. (Γ. Ots, et al) Macromolecule Chem. \ 71 , 150 (1964)) 300 was dissolved in ethyl acetate sorp acetate, and 60 Ketjen Black-5C was added to the solution and dispersed well. This is applied to a disc-shaped carbon fiber with a diameter of 45 cm (Kakuha Manabu Co., Ltd., £ -.715), and the ethyl selone lupe acetate is removed by evaporation. This was immersed in an iodine acetone solution, and [9] iodine was added to 320 to use it as a positive electrode. As the negative electrode, a 0.3 galvanized zinc plate (manufactured by Mitsui Kinzoku Co., Ltd.) was used. The electrolytic solution was a 1M aqueous solution of NCI, which was impregnated into two pieces of glass fiber paper. As a recorder, a Remion C i film made by Asahi Glass was inserted. This was placed between the poles to make a battery. The structure of the battery is shown in FIG. 1 as in Example 1; Experiments conducted under a nitrogen gas stream 2 5 ° C, the discharge time of the initial short-circuit current (/ sc) was measured, it was 9 ² / cm 2. At this time, the open haze pressure was 1.36 ^. The battery was discharged to a final voltage of 0.9 under the condition of a constant current of 2 mA, and then charged and discharged to a final voltage of 1.5. Even after 600 cycles, the energy efficiency and the current efficiency were almost unchanged. The electric capacity after 600 cycles with respect to the initial capacity was 88%. This indicates that this battery is practically at a practical level as a secondary battery. For comparison, Ketchen 'Black! : The battery was made in exactly the same procedure as above except that the cathode mixture without the addition of S-(7) was used.9) Under the same conditions, the initial short-circuit current (/ sc) of the battery during discharge was calculated as follows: The measured value was 10 mΑ / αι ^, and the open-circuit voltage at this time was 1 * 34 4. Further charge / discharge tests were performed. 'Example Ί

Parex resin (trademark of Sohio, USA, sold by Mitsui Toatsu Chemicals, Inc., acrylic acid nitrile, methylacrylate, butadiene copolymer, graft polymer) In a formic acid solution containing 300 ^ ¾! Ketjen's Black Β Β-EC (^ ZO) was added and dispersed well. This is applied to disc-shaped carbon fiber (Kureha Chemical Co., Ltd.-715) with a diameter of 45, and formic acid is removed by natural evaporation method. This was immersed in an iodine-acetone solution to add j-iodine 380 ^, and used as a positive electrode. A 0.3-inch thick zinc plate (made by Mitsui Kinzoku m) was used as the negative electrode. The electrolyte is a 1 molar aqueous solution of, which is impregnated into two pieces of glass fiber paper, during which time the cell is exposed. A selemiion CM ^ membrane made by Asahi Co., Ltd. was sandwiched between them. This was placed between both electrodes to form a battery. The configuration of the battery is the same as in Example 1, as shown in FIG. 1]).

Experiments conducted under a nitrogen gas stream 5 ° C, was measured the initial short-circuit current during discharge was 7 0 mA / cm ^z. The open voltage at this time is 1:35

, Met. The charge-discharge test for charging to a final voltage of ^1.5 After electrostatic discharge to the final voltage of 0. 9 gamma under the conditions of the battery 2 w constant current Ku] returned. Even after 600 cycles, the energy efficiency and the current efficiency were almost unchanged. The electric capacity after 600 cycles with respect to the initial capacity was 85. This indicates that this battery is practically at a practical level as a secondary battery.

For comparison, a battery was prepared in exactly the same procedure as above except that a positive electrode mixture to which Ketjen * Plac- was not added was used. When the initial short-circuit current (/ sc) of the battery at the time of discharge was measured, it was TA / cni ^L. The opening pressure at this time was 1.34. After a charge / discharge test, the battery was charged after discharge, but the voltage rose sharply and could not be charged.

Example 8

Add ェ 9 <D ketchene 'Black KB-EC (trademark of Company A) to an ethyl acetate bath containing 300 W of poly (methyl methacrylate) (average molecular weight: 1,500,000). Well dispersed. The intended diameter ^{4 5} ^ disk-shaped carbon fiber (Kureha of characters Co. ^ - 7 1 5)? A was applied by an acid Echiru the natural evaporation] 9 preparative] excluded. This was immersed in an iodine acetate solution to add iodine 220 ^ and used as a positive electrode. As the negative electrode, a 0.3-thick sub-plate (manufactured by Mitsui Kinzoku Co., Ltd.) was used. The electrolyte is a 1 molar aqueous solution of N, which is impregnated with ^two pieces of glass fiber; paper with ² pieces of water. A selemion membrane made of Asahi Glass (pearl) was inserted as a lator. This was placed between the electrodes to make a battery. The configuration of the battery is as shown in FIG. Experiments conducted under a nitrogen gas stream 2 5 ° C, was measured discharge electricity when the initial short-circuit current (/ sc), was 6 8 A / cm ^z. The open-circuit voltage at this time was 1.36. Discharge the battery to a cut-off voltage of 0.9 under the condition of a constant current of 2 m and then charge it to a cut-off voltage of 5 V. I returned. Even after 600 cycles, the energy efficiency and the current efficiency were almost unchanged. The electric capacity after 600 cycles with respect to the initial capacity was 82. This indicates that this battery is practically in practical use as a secondary battery.

For comparison, a battery was prepared in exactly the same procedure as above except that a positive electrode mixture without the addition of Ketjen * Black KB-EC was used and evaluated under the same conditions. The initial short-circuit current during discharge of the battery (/ sc) was measured and found to be 7 m A / cm ^z. The open circuit voltage at this time was 1.34. After a further charge / discharge test, charging was attempted after discharging, but the voltage rose sharply and charging failed.

Example 9

Dissolve Bolibul Alcohol (made by Kuraray (Δ)) 270 ^ and Volimelamine Resin Cymer 303 (trademark of Mitsui Toatsu Chemicals Co., Ltd.) 30 in water, and add 60 ^ Ketjen 'Black to this aqueous solution. s-(trademark) was added and dispersed well. This is disc-shaped carbon fiber with a diameter of 4.5 (Kure

QMPL The solution was applied to Hana Chemical Co., Ltd. 7 15), water was removed by a natural evaporation method, and heat treatment was performed at 150 ° C. for 40 minutes. This was immersed in an iodine acetone solution to add 9) iodine 360 ^, and used as a positive electrode. The negative electrode used was a 0.3-female thick zinc plate (Mitsui Metals Co., Ltd.) The electrolyte was a 1M aqueous solution of V ^ CZ, which was impregnated into two sheets of glass fiber paper, during which time the separator was used. As shown in Fig. 1, a battery was inserted between both electrodes to form a battery. It belongs to 3ffij.

Experiments carried out at Nozomimoto stream for 2 ⁵ ° C, where the discharge time of the initial short-circuit current (sc) were measured and found to be 3 0 0 mA / cm ^z. The open-circuit voltage at this time was 1.36 F. The battery was discharged to a final voltage of 0.9 under the condition of two constant currents, and then charged and discharged to a final voltage of 1.5. Even after 600 cycles, the energy and current efficiencies changed substantially. The electric capacity after 600 cycles with respect to the initial capacity was 90 °. This indicates that this battery is practically at a practical level as a secondary battery.

For comparison, a battery was prepared in exactly the same manner as above except that a positive electrode mixture without Ketjen Black:-was used. The initial short-circuit current during discharge of the battery (/ SC) was measured and found to be 1 6 mA / an ^z. The opening pressure at this time was 1, 3 4. After further charge / discharge test, after discharge, I tried to charge, It was difficult to charge.

Example 10

To a tetrahydrofuran solution containing vinylpyrrolidone (average molecular weight: 163,000) 300 ^^ was added 60 Ketjen Black: KB-EC (AKZO m) and dispersed well. This is applied to disc-shaped carbon fiber with a diameter of 4.5 (manufactured by Hana Kagaku (Δ)-715), and tetrahydrofuran is removed by natural evaporation method. This was immersed in an iodine acetate solution.] 9 Iodine 420 was added to use as a positive electrode. A 0: 3 female zinc plate (manufactured by Sanban Metal Co., Ltd.) was used as the negative electrode. The electrolyte is a 1 molar Z ^ aqueous solution of CI, which is impregnated with two pieces of paper, two pieces of paper and two pieces of paper. A SELEMION d film made by Asahi Glass (¾) was inserted as a lator. This was placed between the electrodes to make a battery. The battery is the same as in Example 1, as shown in FIG.

Experiments conducted under a nitrogen gas stream 2 5 ° C, was measured the initial short-circuit current se) during discharging was 9 2 τηΑ / αη ^ζ. The open-circuit voltage at this time was 1.36. The battery was discharged to a cutoff voltage of 0.9 under the condition of a constant current of 2 m, and then charged and discharged to charge it to a cutoff voltage of 1.5.

Even after 600 cycles, the energy efficiency and current efficiency were almost unchanged. The electric capacity after 600 cycles with respect to the initial capacity was 86%. This indicates that this battery is practically at a practical level as a secondary battery. For comparison, a battery was prepared in exactly the same procedure as above except that a positive electrode mixture without Ketjen Black KB-EC was added!) And evaluated under the same conditions. The initial short-circuit current during discharge of the battery (/ sc) was measured, was 9 mA / cm ^z. The open circuit voltage at this time was 1.34. In addition, when a charge / discharge test was performed, charging was attempted after discharging, but the voltage rose sharply and charging was not possible. '' Example 1 1

Poly-2-vinyl quince. To a solution of resin (average molecular weight: 80,000) in tetrahydrofuran containing 300 W was added 60 ketjen'black ブラック -ΒC (Hisha trademark), which was well dispersed. This is applied to disk-shaped carbon fiber with a diameter of ^4.5 (Kuwa Chemical Co., Ltd.-T15), and tetrahydralane is spontaneously evaporated! ) Remove. This was immersed in an iodine acetone solution to add iodine 430 to use as a positive electrode. The negative electrode used was a 0.3-inch thick zinc plate (manufactured by Mitsui Kinzoku Co., Ltd.). The electrolyte is

This was impregnated with 2 pieces of glass fiber; F paper 2 with a 1 mol Z aqueous solution of V ₄ C, and on that day, a selemion membrane manufactured by Asahi Corporation was sandwiched as a seha ⁰ . This was placed between both electrodes to form a battery. The configuration of the battery is the same as that shown in FIG.

The experiment was carried out at 25 ° C under a nitrogen stream, and the initial short-circuit current (sc) at the time of discharge was measured to be 95 mA / ctn ^2- . The open-circuit voltage at this time: 1. was ³ 6 ^Γ. Discharge the battery to a final voltage of 0.9 under two constant current conditions.

O PI And D Kaee rather the charge-discharge test for charging to a final voltage of ^1.5 After electrodeposition.

Even after 600 cycles, the energy efficiency and the current efficiency were almost unchanged. The electric capacity after 600 cycles with respect to the initial capacity was 88%. This indicates that this battery is practically at a practical level as a secondary battery.

For comparison, a battery was prepared in exactly the same procedure as above except that a positive electrode mixture to which Ketchi's' Black -C was added was used. The evaluation was performed under the same conditions. The initial short-circuit current during discharge of the battery (/ sc) was measured and found to be 1 0 A / cnt ^z. The open circuit voltage at this time was L34 4. After a further charge / discharge test, we tried to charge the battery after discharging, but the voltage was too high to charge.

Example 1 2

Nylon-6 (made by Δ) containing 20 weights of Ketjen Black is converted into a carbon-like carbon whip (4.5 cm in diameter) (made by Kureha Chemical (ft)-715) Applied. This was immersed in an iodine acetate solution to add iodine 460 to use as a positive electrode 10. As the negative electrode, a 0.3 mm thick zinc sheet (made by Sanban Metal Co., Ltd.) was used. 1 molar aqueous solution of electrolyte N ^ C, which 2. glass fiber paper to 2 impregnated in, Serra ⁰ Les therebetween - inserting the various 1-by-exchange membrane as data. This was assembled into a battery using a rubber packing and a support as shown in FIG.

Save real using the ¾ ponds performed at ² 5 ° C, elapsed and the electromotive force of time (Open circuit voltage) was measured. The results are shown in Table 1.

Seh for comparison. When a writer is not used and Kuraray Co., Ltd. P-type seha. Table 1 also shows the results obtained when a writer (vinylon S ^ N) was used.

* The initial value of electromotive force is 1.32 to 1.35 5

As is evident from Table 1, Seha. If you did not use the regulator, an electromotive force is ^1.3 2 in just or two days; I. ³ sharply reduced from 5 to ^0.9, for flights to or ^ Ρ made separator one data In that case, of course, although it is better than this, the electromotive force will drop to 0.5 after 10 days, and it will not be practical any longer.

On the other hand, for example, SERAMION cation exchange membrane (manufactured by Asahi Glass Co., Ltd.) was used. Table 1 shows that when used as a rake, the electromotive force hardly decreased even after 300 days, and the battery life was greatly extended.

OMPI

WIPO j ejVATio ^ Example 13

Ketjen. Black is mixed with Euroid * 320 (manufactured by Mitsui Toatsu Chemicals, Inc.), which is the initial reaction product of urea resin, to a weight of 15%, and the hardening agent is added to the mixture 500 ^. and无分kneaded to 1 2 V Shio漦one drop as it diameter ⁴ ⁵ of the disk-shaped carbon fiber (Kureha chemical Co., Ltd. - 7 1 5). was applied and Kati spoon to. This was immersed in an iodine-acetone solution, and] iodine was added to form a positive electrode. As the negative electrode using ^0.3 KyoAtsuA錯板(manufactured by Mitsui Metal Co.). The electrolyte is a 1 molar aqueous solution of N, which is impregnated with two pieces of glass bran fiber paper, during which time the cell is washed. Various kinds of positive ion exchange membranes were sandwiched between them. This was placed between the electrodes to form a battery. Battery configuration is implemented! As shown in Fig. 1, there is the one shown in Fig. 1.

A storage experiment using this battery was performed at 25 ° C, and the relationship between the passage of time and the electromotive force (open circuit voltage) was measured. The results are shown in Table 2.

Contact, Seh for comparison. Shown in Table 2 together also results using the cases have to a stool, single-data and Kuraray (supporting post) ¾ gamma system Serra ⁰ regulator (Vinylon TN).

Table 2

* The initial value of the electromotive method is 1.3 1 to: I. 3 5

As is evident from Table 2, when the separator was not used, the electromotive force suddenly dropped from 1.31 to L.35 to 0.82 in just two days. After 5 days, it decreased to 0.30Γ. Also made by セ. If a writer is used, of course the j9 is also improved, but after 10 days the electromotive force drops to 0.4 mm, which is not practical.

On the other hand, for example, when a selemion cation exchange membrane (produced by Asahi Glass Co., Ltd.) is used as a separator, the electromotive force hardly decreases even after ₃₀ days, and the battery life is dramatically improved. It can be seen from Table 2 that

Example 14

The iodine Z subcomplex battery (using a selemion-ion ion exchange membrane) obtained by the method of Example 12 was subjected to one constant-current charge / discharge. ⁵ hours discharge and 5 o'clock charge 1 cycle 1 o'clock As a result of the discussion, 300 cycles

OMPI The change in electromotive force was constant without losing battery characteristics even by eyes. This characteristic indicates that this battery has excellent properties as a rechargeable secondary battery, that is, a storage battery.

[Industrial applicability]

The battery of the present invention has a high output and a low internal resistance. In addition, even when iodine fixed to the positive electrode mixture is almost completely released due to the progress of discharge, the conductivity is hardly reduced, so that the charging operation can be easily performed.

In addition, the battery characteristics are not lost even if the charge / discharge cycle is repeated many times (for example, 300 cycles), and almost no electromotive force occurs even after a long period (for example, 300 days). Battery life has not been reduced, and the battery life has been dramatically increased.

The battery of the present invention can be used as a primary battery, or more preferably, as a secondary battery, and includes a VTR communication device, a calculator, a clock, a computer, and

^ It is suitable for use as a backup power supply for equipment (such as a word processor), an emergency power supply, and a solar system battery such as a solar battery.

ΟΜΡΓ

'L ^w O

Claims

The scope of the claims

1. Positive complex adduct of iodine and a polymer capable of forming a complex adduct with iodine and Z or a composition obtained by dispersing iodine in the polymer; the main component of the S mixture A battery, wherein the positive electrode mixture contains carbon in a dispersed state.

2. The battery according to claim 1, wherein the polymer is a group consisting of polynamide, poly (meth) acrylamide, polyurethane, polybutyl alcohol, and polyether. .

3. The claim wherein the carbons are selected from the group consisting of carbon black, acetylene black, dalaphite, and ketchup plaque.

Battery according to claim 1.

4. The battery according to claim 3, wherein the carbon has a shape that is easily dispersed, such as a powder, a scale, or a short fiber.

5. The battery according to claim 3, wherein 1 to 60 carbons are contained in the polymer.

6. The battery according to claim 1, wherein the negative electrode metal is selected from the group consisting of lithium, zinc, power, magnesium, and aluminum.

7. The battery of claim 1, wherein the battery is a single battery.

8. The battery according to any one of claims 1 to 6 wherein the battery is a secondary battery The battery according to 1.

9. The battery according to claim 8, wherein the battery is a secondary battery having an electrolyte solution.

1 0. The cation exchange membrane is Sehha. 10. The battery according to claim 9, wherein the battery is inserted into the electrolyte solution as a generator.

1 1. As electrolyte solution, ammonium chloride, sodium chloride, sodium chloride

&, A group consisting of NaOH's rhodium, potash, potassium iodide and lithium iodide] 5. An electrolyte solution selected from the group consisting of: battery.

The battery according to claim 10, wherein the I% electrolytic poor solution is used by being impregnated on a porous support.

Ο ΡΓ E D-】